EP0643752A1 - Dentalharzmasse auf basis von polymeribaren polysiloxamen - Google Patents

Dentalharzmasse auf basis von polymeribaren polysiloxamen

Info

Publication number
EP0643752A1
EP0643752A1 EP92922122A EP92922122A EP0643752A1 EP 0643752 A1 EP0643752 A1 EP 0643752A1 EP 92922122 A EP92922122 A EP 92922122A EP 92922122 A EP92922122 A EP 92922122A EP 0643752 A1 EP0643752 A1 EP 0643752A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
general formula
nhc
aryl
radicals
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP92922122A
Other languages
English (en)
French (fr)
Other versions
EP0643752B1 (de
EP0643752A4 (de
Inventor
Werner Storch
Herbert Wolter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6442372&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0643752(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0643752A4 publication Critical patent/EP0643752A4/de
Publication of EP0643752A1 publication Critical patent/EP0643752A1/de
Application granted granted Critical
Publication of EP0643752B1 publication Critical patent/EP0643752B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/20—Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A61K6/896—Polyorganosilicon compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S528/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S528/92—Polymers useful for replacing hard animal tissues, e.g. dentures, bones

Definitions

  • the invention relates to a resinous dental composition, which is self-curing, photochemically or thermally curable in the presence of initiators, based on polymerisable polysiloxanes, to a process for its preparation and to its use for the preparation of pasty dental materials, which are self- curing, photochemically or thermally curable in the presence of initiators, which are composed of one or more resinous dental compositions and optionally of one or more finely divided fillers and/or customary additives.
  • Suitable additives are, for example, pigments, stabilisers, plasticisers or impact strength enhancers.
  • dental material includes, for example, filling materials for looking after carious defects or other dental defects in the oral cavity, inlays, crown and bridge materials, facings, sealing and protective coating compositions, synthetic fixing materials for fixing inlays or crowns and bridges, stump building-up materials, prosthetic materials, compositions for the production of artificial teeth, and adhesion promoters for dental filling materials.
  • Suitable monofunctional esters of methacrylic acid are, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-hexyl methacrylate and 2-hydroxyethyl methacrylate.
  • polyfunctional esters of methacrylic acid with relatively high molecular weights have commonly been employed, such as, for example, ethylene glycol dimethacrylate, butanediol 1,4-dimethacrylate, triethylene glycol dimethacrylate, dodecanediol-l,12-dimethacrylate, dodecanediol 1,10-dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, trimethylolpropane trimethacrylate , 2 ,2-bis[p-( 7-meth-acryloxy- ⁇ -hydroxy- propoxy)-phenyl]-propane, 2 ,2-bis[p-( ⁇ -hydroxyethoxy)- phenyl]propane dimethacrylate (bis-GMA) , the diadduct of hydroxyethyl methacrylate and trimethylhexamethylene diisocyanate and the diad
  • methyl methacrylate which are used as prosthetic bases, crown and bridge resins or as filling resins, do present outstanding advantages with respect to their workability, their aesthetic appearance, their stability in the oral area etc.
  • these materials have poor mechanical strengths, it may happen that a breakage occurs in the production of a prosthesis after polymerisation in a plaster of Paris mould during removal from this mould, that the prosthesis breaks in the mouth or if it is unintentionally dropped.
  • materials for dental applications can be cured in various ways.
  • dental filling materials both as photochemically curing and as self-curing (autopolymerising) compositions.
  • the photochemically curing compositions contain photoinitiators such as benzoin alkyl ethers, benzil monoketals, acylphosphine oxides or aliphatic or aromatic 1,2-diketo compounds, such as, for example, camphorquinone, and polymerisation accelerators such as aliphatic or aromatic tertiary amines, for example N,N- dimethyl-p-toluidine or triethanolamine, or organic phosphites, and cure on irradiation with UV or visible light.
  • photoinitiators such as benzoin alkyl ethers, benzil monoketals, acylphosphine oxides or aliphatic or aromatic 1,2-diketo compounds, such as, for example, camphorquinone
  • polymerisation accelerators such as aliphatic or aromatic tert
  • the self-curing dental materials are composed as a rule of a catalyst and a base paste, each of which contains the component of a redox system, and which polymerise on mixing both components.
  • One component of the redox system is usually a peroxide, such as, for example, dibenzoyl peroxide, the other is usually a tertiary aromatic amine, such as, for example, N,N-dimethy1-p-toluidine.
  • dental materials such as prosthetic plastics or synthetic compositions for the production of artificial teeth can be polymerised under the action of heat.
  • Initiators used here are as a rule peroxides such as dibenzoyl peroxide, dilauryl peroxide or bis(2,4-dichlorobenzoyl peroxide).
  • Dental materials furthermore as a rule contain pigments which - added in a small amount - are used to bring the colour of the dental materials into line with the various shadings of natural teeth.
  • Suitable pigments are, for example, iron oxide black, iron oxide red, iron oxide yellow, iron oxide brown, zinc oxide and titanium oxide.
  • Dental materials usually also contain organic or inorganic fillers. This is done in order to reduce the shrinkage in volume of the resinous dental composition during polymerisation. Pure, monomeric methyl methacrylate shrinks, for example, during polymerisation by about 20% by volume. By addition of about 60% by weight of solid methyl methacrylate polymer, the shrinkage can be reduced to about 5 to 7% by volume (DE Patent 2,403,211).
  • organic fillers are obtained by preparing a polymer which is essentially composed of methacrylic acid esters and is non-crosslinked or crosslinked. This polymer optionally contains surface-treated fillers. If it is prepared as a polymer, it can be added to the resinous dental composition in this form; on the other hand if it is prepared in compact form by polymerisation in substance, it must first be ground to give a so-called chip polymer before incorporation in the resinous dental composition.
  • preformed polymers are homopolymers of methyl methacrylate or, preferably non-crosslinked, copolymers of methyl methacrylate having a low content of esters of methyacrylic acid or of acrylic acid with 2 to 12 C atoms in the alcohol component, expediently in the form of a bead polymer.
  • suitable polymers are non- crosslinked products based on polyurethanes, polycarbonates, polyesters and polyethers.
  • dental filling materials based on polymerisable (meth)acrylic acid esters are disclosed as a resinous dental composition, i.e. as binders which contain finely ground inorganic/organic polymers based on polysiloxanes as fillers.
  • these inorganic/organic polymers are added in finely ground form to the resinous dental composition, together with other components, as a filler.
  • Inorganic fillers are, for example, finely ground glasses or quartz having mean particle sizes between about 1 and 10 ⁇ m and highly disperse Si02 having mean particle sizes between about 10 and 400 nm.
  • the glasses are preferably aluminium silicate glasses, which can be doped with barium, strontium or rare earths (DE Patent 2,458,380).
  • the inorganic filler is as a rule silanised before mixing with the monomers for better binding to the organic matrix.
  • the inorganic fillers are coated with silane coupling agents (as adhesion promoters) which usually have a polymerisable double bond for reaction with the monomeric esters of methacrylic acid.
  • silane coupling agents are, for example, vinyl trichlorosilane, tris(2-methoxyethoxy)vinylsilane, tris(acetoxy)vinylsilane and 3-methacryloyloxypropyl- trimethoxysilane.
  • filling materials composed of fillers and polymerisable compounds, the so-called “composites”, have in particular recently gained increasing importance in dental medicine. These are composed of an inorganic or organic filler and of a curable organic matrix. In this way, the fillers cause a decrease in the shrinkage on polymerisation of the resultant dental material and a reinforcement of the organic polymer structure. Very generally, it can be said that improved mechanical properties and a reduced shrinkage on curing can be achieved by as high a content as possible of fillers in the dental materials.
  • the highest amount of fillers to be employed is dependent, however, on the properties of the monomers employed in the resinous dental composition.
  • a highly glossy and completely homogeneous surface of the filling material is to be required in order that the filling can no longer be differentiated from the surrounding, absolutely smooth, natural dental enamel. Furthermore, this highly glossy filling surface must retain its character long-term. A highly smooth filling surface is therefore also important in order that plaque or discolouring media do not find any mechanical anchorage sites.
  • the property of high gloss polishing ability is produced by the addition of fillers, since the customary resinous dental compositions employed as binders are not polishable after their curing.
  • DE 3,913,250 Al and DE 3,913,252 Al disclose dental materials which are curable to give a composition which can be polished to a high gloss. This high gloss polishing ability is achieved by the addition of finely divided organopolysiloxanes as a filler.
  • a further weak point of the conventional composite materials is their poor abrasion behaviour.
  • a dental material and in particular of a dental filling material are its X-ray opacity and its adhesion to enamel and to dentine, where the adhesive force to enamel and to dentine should be larger than the shrinkage forces.
  • the X-ray opacity is set by the type and amount of the fillers and it is usually achieved by addition of Ba, Sr, Ti or Zr components.
  • the adhesive force to dentine is inadequate even when using dentine adhesives.
  • the object of the present invention was therefore to make available a resinous dental composition which is self- curing, thermally or photochemically curable, which is simple to process, which on curing undergoes no shrinkage in volume or only a slight shrinkage in volume and which after curing even without addition of fillers should have the following properties: - a high resistance to abrasion, a high dimensional stability, a low thermal expansion coefficient, a high radioopacity, a large adhesion force to enamel and dentine and a good polishing ability.
  • resinous dental compositions should either be employable as such as dental materials, or they should be able to be processed to give the dental materials mentioned at the beginning, with the addition of further components, such as, for example, of further resinous compositions, or of fillers, pigments, initiators, stabilisers, plasticisers or impact strength enhancers.
  • the resinous dental compositions should be employable as or in mono- or multicomponent systems.
  • resinous dental compositions based on polymerisable polysiloxanes which are self-curing, photochemically or thermally curable in the presence of one or more initiators, and which are obtainable by hydrolytic condensation of one or more hydrolytically condensable compounds of silicon and if desired other elements of the group comprising B, Ba, Ti, Zr, Al, Sn, the transition metals, the lanthanides and the actinides, and/or precondensates derived from the abovementioned compounds, if appropriate in the presence of a catalyst and/or of a solvent, by the action of water or moisture, 1 to 100 mol%, preferably 5 to 100 mol%, based on monomeric compounds, of silanes of the general formula (I)
  • radicals X, Y and R are identical or different and have the following meaning:
  • R alkyl, alkenyl, aryl, alkylaryl or arylalkyl
  • X hydrogen, halogen, hydroxyl, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or NR' 2.
  • R 1 hydrogen, alkyl or aryl
  • radicals A, R, R 2 and X are identical or different and have the following meaning:
  • R alkyl, alkenyl, aryl, alkylaryl or arylalkyl
  • R2 alkylene, arylene or alkylenearylene
  • the resinous dental compositions according to the invention form polymers after curing thereof and even without addition of fillers, which have excellent resistances to abrasion and dimensional stabilities, which have low thermal expansion coefficients and high radioopacities, and which exhibit a very large adhesive force to enamel and dentine and very good polishing abilities.
  • the resinous dental compositions according to the invention depending on the silanes employed, undergo only a very low, no or even a negative shrinkage in volume on curing.
  • silanes of the general formulae (I) and (II) are hydrolysable and polymerisable, the radicals X being hydrolysable and the radicals B and Y being polymerisable and in each case at least one radical B, X and Y having the abovementioned meaning being present in the silanes of the general formulae (I) and (II) .
  • the alkyl radicals are, for example, straight-chain, branched or cyclic radicals having 1 to 20, preferably having 1 to 10, carbon atoms, and particularly preferably are lower alkyl radicals having l to 6 carbon atoms. Specific examples are methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t- butyl, i-butyl, n-pentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, dodecyl and octadecyl.
  • alkenyl radicals are, for example, straight- chain, branched or cyclic radicals having 2 to 20, preferably having 2 to 10, carbon atoms, and particularly preferably are lower alkenyl radicals having 2 to 6 carbon atoms, such as, for example, vinyl, allyl or 2-butenyl.
  • Preferred aryl radicals are phenyl, biphenyl and naphthyl.
  • the alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl and amino radicals are preferably derived from the abovementioned alkyl and aryl radicals.
  • Specific examples are methoxy, ethoxy, n- and i-propoxy, n-, i-, s- and t-butoxy, methylamino, ethylamino, dimethylamino, diethylamino, N- ethylanilino, acetoxy, propionyloxy, methylcarbonyl, ethylcarbonyl, methoxycarbonyl, ethoxycarbonyl, benzyl, 2- phenylethyl and tolyl.
  • the said radicals can optionally carry one or more substituents, for example halogen, alkyl, hydroxyalky1, alkoxy, aryl, aryloxy, alkylcarbonyl, alkoxycarbonyl, furfuryl, tetrahydrofurfuryl, amino, alkylamino, dialkylamino. trialkylammonium, amido, hydroxyl, formyl, carboxyl, mercapto, cyano, isocyanato, nitro, epoxy, S0 3 H and PO4H2.
  • substituents for example halogen, alkyl, hydroxyalky1, alkoxy, aryl, aryloxy, alkylcarbonyl, alkoxycarbonyl, furfuryl, tetrahydrofurfuryl, amino, alkylamino, dialkylamino. trialkylammonium, amido, hydroxyl, formyl, carboxyl, mercapto, cyano, isocyanato, nitro
  • halogens fluorine, chlorine and bromine are preferred.
  • substituted or unsubstituted 1,4,6-tri- oxaspiro[4.4]nonane groups are bonded to the Si atom via alkylene or via alkenylene radicals, which can be interrupted by ether or ester groups.
  • alkylene or via alkenylene radicals which can be interrupted by ether or ester groups.
  • ring system which is derived from 7-butyrolactone
  • substituents can be hydrogen, halogen or hydroxyl, alkyl, alkenyl, aryl, alkylaryl, arylalkyl, alkylcarbonyl or alkoxycarbonyl groups. Actual examples of these are
  • silanes of the formula (I) are:
  • R, R 2 , A, n, k, 1 and x are defined as follows:
  • X (C ⁇ -C )-alkoxy, preferably methoxy and ethoxy, or halogen, preferably chlorine?
  • R (C- L -C 4 )-alkyl, preferably methyl and ethyl;
  • R2 (C ⁇ -C ⁇ )-alkylene, preferably methylene and propylene;
  • 1 0 or 1, preferably 1;
  • the structural unit having the index x is selected from triethoxysilyl, methyl-diethoxysilyl, methyldichlorosilyl, 3-methyldimethoxy-silylpropylthio, 3- triethoxysilylpropylthio, ethoxydimethylsilylmethylthio and methyldiethoxysilylmethylthio.
  • B is preferably derived from a substituted or unsubstituted compound B 1 having two or more acrylate and/or methacrylate groups.
  • Compounds of this type are designated in the following as (meth)acrylates. If the compound B' is substituted, the substituents can be selected from among the abovementioned substituents.
  • Specific examples of compounds of this type are the following (meth)acrylates: H 3 C 0 O CH 3 H 3 C 0 O CH 3 J I
  • CH 2 C-C-NH-CH 3 -CH2-NH-C-C-CH2
  • CH 2 C-C-NH-CH -NH-C-C-CH 2
  • CH 2 C-C ( -0-CH 2 -CH 2 ) 2 -0-C-C-CH 2
  • Preferred acrylates are, for example, the acrylic acid esters of trimethylolpropane, pentaerythritol and dipentaerythritol. Actual examples of these are tri ⁇ methylolpropane triacrylate (TMPTA) , pentaerythritol triacrylate (PETA) , pentaerythritol tetraacrylate and dipentaerythritol pentaacrylate.
  • TMPTA tri ⁇ methylolpropane triacrylate
  • PETA pentaerythritol triacrylate
  • pentaerythritol tetraacrylate pentaerythritol pentaacrylate.
  • C2 ⁇ Cg- alkanediols for example ethylene glycol, propylene glycol, butylene glycol, 1,6-hexanediol
  • silanes of the general formula (I) are prepared, for example, by reaction of silanes of the general formula (IV)
  • radicals X, Y 1 and R in the general formula (IV) are identical or different, X, R, n and m have the same meaning as in the silanes of the general formula (I), and Y 1 is a radical which represents a substituted oxirane ring. That stated above for the silanes of the general formula (I) applies to the possible embodiments of the radicals X and R.
  • silanes of the general formula (IV) are: glycidoxymethyltrimethoxysilane. glycidoxy ethyltriethoxysilane, 2-glycidoxyethyltri- ethoxysilane, 2-glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy-propyltrie- thoxysilane, 3-glycidoxypropyl-tri(methoxyethoxy)silane, 3- glycidoxypropyltriacetoxy-silane, 4-glyci-doxy- butyltrimethoxysilane , 4-glycidoxy-butyltrieth-oxysilane, glycidoxymethyl(methyl)-dimethoxysilane, glycidoxy ⁇ methyl(ethyl)dimethoxysilane, glycidoxymethyl(phenyl)- dimethoxysi
  • Silanes of the general formula (IV) are commercially available, thus, for example, 3-glycidoxy- propyldimethylethoxysilane, (3-glycidoxypropyl)-methyldi- ethoxysilane, 3-glycidoxypropyl-methyldiisopropenoxy-silane, (3-glycidoxypropyl)-trimethoxysilane, 2-(3,4-epoxycyclohexyl)- ethyltri ethoxysilane or [2-(3,4-epoxy-4-methyl- cyclohexyl)propyl]methyldiethoxy-silane at ABCR GmbH & Co.KG (Karlsruhe) .
  • silanes can be converted with 7- butyrolactones into the corresponding spirosilanes of the general formula (I) .
  • Suitable 7-butyrolactones for preparation of the spirosilanes of the general formula (I) are unsubstituted 7- butyrolactone, and also 7-butyrolactones substituted by hydroxyl, alkyl, alkenyl, aryl, alkylaryl, arylalkyl, alkylcarbonyl or alkoxycarbonyl groups.
  • the alkyl radicals are, for example, straight-chain, branched or cyclic radicals having 1 to 10 C atoms, and particularly preferably are lower alkyl radicals having 1 to 6 C atoms. Specific examples are methyl, ethyl, n-propyl, i- propyl, n-butyl, s-butyl, t-butyl, i-butyl, n-pentyl and n- hexyl.
  • alkenyl radicals are, for example, straight- chain, branched or cyclic radicals having 2 to 10 carbon atoms, and particularly preferably are lower alkenyl radicals having 2 to 6 carbon atoms, such as, for example, vinyl, allyl or 2- butenyl.
  • Lewis acids are BF 3 ⁇ t 2 0, A1C1 3 or SnCl 4 .
  • silanes of the general formula (IV) are reacted with the 7-butyrolactones to give the spirosilanes of the general formula (I) with exclusion of water, if appropriate in an inert solvent.
  • known techniques such as, for example, high vacuum distillation, are used.
  • silanes according to the general formula (II) can be prepared, for example, by
  • silanes of the general formulae (V) to (VII) are either commercially available or can be prepared by known methods; cf. W. Noll, "Chemie und Technologie der Silicone” (Chemistry and Technology of Silicones) , Verlag Chemie GmbH, Weinheim/Bergstrasse (1968) . In addition, reference is made to German Patent Application P 40 11 044.3.
  • the spirosilanes of the general formula (I) are stable compounds which are hydrolysable and condensable in basic medium without the spiro complex being prematurely opened.
  • German Patent Application P 41 25 201 reference is made to German Patent Application P 41 25 201.
  • the cured resinous dental compositions thus form an inorganic/organic matrix in which, when required, other components, such as, for example, fillers or pigments, can be incorporated.
  • the spirosilanes of the general formula (I) and/or the silanes of the general formula (II) are hydrolysed and polycondensed by the action of water or moisture, if appropriate with the addition of other co-condensable components and if appropriate in the presence of a catalyst and/or of a solvent.
  • This polycondensation is preferably carried out by the sol-gel process, as is described, for example, in DE-A1 2,758,414, 2,758,415, 3,011,761, 3,826,715 and 3,835,968, and takes place in the presence of spiro compounds (silanes of the general formula (I) , copolymerisable spiro-orthoesters , spiro-orthocarbonates, bicyclic spiro- orthoesters or methacryloyl spiro-orthoesters) , preferably in basic medium, otherwise it can also be carried out in acidic medium.
  • spiro compounds silanes of the general formula (I) , copolymerisable spiro-orthoesters , spiro-orthocarbonates, bicyclic spiro- orthoesters or methacryloyl spiro-orthoesters
  • the resinous dental composition according to the invention i.e. the polycondensate of the silanes of the general formulae (I) and/or (II) and if desired of further polycondensable components, is polymerised, if appropriate after addition of other copolymerisable components and/or after addition of fillers and/or of other additives, if appropriate in the presence of one or more initiators.
  • the polymerisation can be carried out, for example, thermally or photochemically using customary methods.
  • the inorganic network is responsible for the fact that the cured resinous dental composition, entirely without the addition of fillers, already has an excellent resistance to abrasion, dimensional stability, polishing ability and adhesive force and a low thermal expansion coefficient, and the construction of the organic network causes the low or even negative shrinkage in volume.
  • the change in volume during the curing can be suited to the requirements of the particular application case.
  • the resinous dental compositions according to the invention comprise 1 to 100 mol%, preferably 5 to 100 mol%, based on monomeric compounds, of silanes of the general formulae (I) and/or (II) .
  • silanes of the general formulae (I) and/or (II) .
  • still other hydrolytically condensable compounds of silicon, boron, barium, aluminium, titanium, zirconium, tin, the transition metals, the lanthanides or actinides can be employed for the preparation of the resinous dental composition according to the invention.
  • These compounds can either be used as such or even in pre- condensed form. It is preferred if at least 10 mol%, in particular at least 80 mol% and specifically at least 90 mol%, based on monomeric compounds, of the starting materials used for preparation of the resinous dental compositions according to the invention are silicon compounds.
  • the resinous dental compositions according to the invention are based on at least 5 mol%, for example 25 to 100 mol%, in particular 50 to 100 mol% and specifically 75 to 100 mol%, in each case based on monomeric compounds, of one or more of the silanes of the general formulae (I) and/or (II) .
  • hydrolytically condensable silicon compounds other than silanes of the general formulae (I) and (II) which can optionally be employed, those of the general formula (III)
  • R alkyl, alkenyl, aryl, alkylaryl or arylalkyl
  • R» ' alkylene or alkenylene, where these radicals can be interrupted by oxygen or sulphur atoms or NH groups,
  • silanes are described, for example, in DE 3,407,087 C2.
  • the alkyl radicals are, for example, straight-chain, branched or cyclic radicals having 1 to 20, preferably having 1 to 10, carbon atoms, and particularly preferably are lower alkyl radicals having 1 to 6 carbon atoms. Specific examples are methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t- butyl, i-butyl, n-pentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, dodecyl and octadecyl.
  • alkenyl radicals are, for example, straight- chain, branched or cyclic radicals having 2 to 20, preferably having 2 to 10, carbon atoms, and particularly preferably are lower alkenyl radicals having 2 to 6 carbon atoms, such as, for example, vinyl, allyl or 2-butenyl.
  • Preferred aryl radicals are phenyl, biphenyl and naphthyl.
  • alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl and amino radicals are preferably derived from the abovementioned alkyl and aryl radicals. Specific examples are methoxy, ethoxy, n- and i-propoxy, n- f i-, s- and t-butoxy, methylamino, ethylamino, dimethylamino, diethylamino, N- ethylanilino , acetoxy, propionyloxy, methylcarbonyl , ethylcarbonyl, methoxycarbonyl, ethoxycarbonyl, benzyl, 2- phenylethyl and tolyl.
  • the said radicals can optionally carry one or more substituents, for example halogen, alkyl, hydroxyalkyl, alkoxy, aryl, aryloxy, alkylcarbonyl, alkoxycarbonyl, furfuryl, tetrahydrofurfuryl, amino, alkylamino, dialkylamino, trialkylammonium, amido, hydroxyl, formyl, carboxyl, mercapto, cyano, nitro, epoxy, S0 3 H and PO 4 H2.
  • substituents for example halogen, alkyl, hydroxyalkyl, alkoxy, aryl, aryloxy, alkylcarbonyl, alkoxycarbonyl, furfuryl, tetrahydrofurfuryl, amino, alkylamino, dialkylamino, trialkylammonium, amido, hydroxyl, formyl, carboxyl, mercapto, cyano, nitro, epoxy, S0 3 H and PO 4
  • halogens fluorine, chlorine and bromine are preferred.
  • hydrolytically condensable silanes of the general formula (III) are:
  • CH 2 CH-Si-(OC 2 H 5 ) 3
  • CH 2 CH-Si-(OC 2 H 4 OCH 3 ) 3
  • CH 2 CH-Si-(OOCCH 3 ) 3
  • hydrolysable aluminium compounds optionally employed, those are particularly preferred which have the general formula (VIII)
  • radicals R ⁇ which can be identical or different, are selected from halogen, alkoxy, alkoxycarbonyl and hydroxyl.
  • R ⁇ which can be identical or different, are selected from halogen, alkoxy, alkoxycarbonyl and hydroxyl.
  • chelate ligands for example acetylacetone or acetoacetic acid ester, acetic acid
  • aluminium compounds are the aluminium alkoxides and halides. In this connection, the following may be mentioned as actual examples * .
  • Suitable hydrolysable titanium or zirconium compounds which can optionally be employed are those of the general formula (IX)
  • M denotes Ti or Zr
  • y is an integer from 1 to 4, in particular 2 to 4
  • z represents 0, 1, 2 or 3, preferably 0, 1 or 2
  • X and R are defined as in the case of the general formula (I) .
  • the compounds of the formula (IX) are those in which y is equal to 4.
  • complexed Ti or Zr compounds can also be employed.
  • Additional preferred complexing agents here are acrylic acid and methacrylic acid.
  • TiCl 4 Ti(0C 2 H 5 ) 4 , Ti(OC 3 H 7 ) 4 , Ti(0-i-C 3 H 7 ) 4 , Ti(0C 4 H 9 ) 4 , Ti(2-ethylhexoxy)4, ZrCl4, Zr(OC 2 H5) 4 , Zr(OC 3 H 7 )4, Zr(0-i-C 3 H 7 )4, Zr(OC 4 H 9 ) , Zr(2-ethylhexoxy)4, ZrOCl 2 .
  • hydrolysable compounds which can be employed for the preparation of the resinous dental compositions according to the invention are, for example, boron trihalides and boric acid esters, such as, for example, BC1 , B(OCH 3 )3 and
  • B(OC 2 H5) 3 tin tetrahalides and tin tetraalkoxides, such as. for example, SnCl 4 and Sn(OCH 3 ) 4 and barium compounds of the general formula BaR°2, in which R° represents alkoxy or acyloxy.
  • R° represents alkoxy or acyloxy.
  • Actual examples are Ba(OCH 3 ) 3 , Ba(OC 2 H 5 ) 3 or Ba(0C0CH 3 ) .
  • the resinous dental composition according to the invention it is possible to incorporate heavy elements, such as, for example, Zr, Ti or Ba into the resinous dental composition according to the invention in such a way that these are uniformly incorporated into the inorganic/organic network after curing.
  • the X-ray opacity of the resinous dental composition according to the invention is increased compared to the resinous dental compositions according to the prior art, and dental materials based on the resinous dental compositions according to the invention are detectable in the X-ray image. This is of particular importance, for example in dental fillings.
  • the X-ray opacity of the resinous dental compositions according to the invention can also be increased by employing, for example, silanes of the general formula (II) whose radical B is derived from a bromine-substituted compound B 1 .
  • Compounds B' of this type have already been enlarged upon in the description of the silanes of the general formula (II) .
  • Br- or I-substituted, hydrolysable silanes so that as a result of hydrolytic condensation the halogen is incorporated into the inorganic network.
  • the resinous dental compositions according to the invention can be prepared in the manner customary in the field of poly(hetero)condensates. If silicon compounds are virtually exclusively employed, the hydrolytic condensation can in most cases be carried out by directly adding the necessary water at room temperature or with slight cooling to the silicon compounds to be hydrolysed, which are either present as such or dissolved in a suitable solvent, (preferably with stirring and in the presence of a hydrolysis and condensation catalyst) and afterwards stirring the resulting mixture for some time (one hour to several hours) .
  • the hydrolysis is as a rule carried out at temperatures between -20 and 130"C, preferably between 0 and 30"C or the boiling point of the solvent optionally employed.
  • the best manner of adding the water in particular depends on the reactivity of the starting compounds employed.
  • the dissolved starting compounds can be slowly added dropwise to an excess of water or water is added in one portion or in portions to the optionally dissolved starting compounds. It may also be useful not to add the water as such, but to introduce it into the reaction system with the aid of water- containing organic or inorganic systems.
  • the introduction of the amount of water into the reaction mixture with the aid of moisture-loaded adsorbents, for example molecular sieves, and water-containing organic solvents, for example 80% strength ethanol, has proven particularly suitable.
  • the addition of water can also be carried out by means of a chemical reaction in which water is set free during the course of the reaction. Examples of this are esterifications.
  • ketones preferably lower dialkyl ketones, such as acetone or methyl isobutyl ketone
  • ethers preferably lower dialkyl ethers, such as diethyl ether or dibutyl ether, THF
  • amides, esters in particular ethyl acetate, dimethylformamide, amines, in particular triethylamine, and mixtures thereof are also suitable.
  • the hydrolysis is preferably carried out in a medium which is basic with respect to these silanes.
  • a basic solvent such as, for example, triethylamine
  • basic hydrolysis and condensation catalysts such as, for example, NH3, NaOH, KOH, ethylimidazole, etc.
  • the starting compounds do not necessarily already all have to be present at the start of the hydrolysis (polycondensation) , but in certain cases it can even prove advantageous if only a part of these compounds is first brought into contact with water and the remaining compounds are added later.
  • the addition of water can be carried out in several steps, for example in three steps.
  • a tenth to a twentieth of the amount of water required for hydrolysis can be added.
  • the condensation time depends on the respective starting components and their proportions, the catalyst optionally used, the reaction temperature, etc.
  • the polycondensation is carried out at normal pressure, but it can also be carried out at elevated or at reduced pressure.
  • the polycondensate thus obtained can either be employed as a resinous dental composition as such or after partial or nearly complete removal of the solvent used or of the solvent formed during the reaction and can be processed to give pasty dental materials which are photochemically and/or thermally curable in the presence of one or more initiators.
  • the reaction mixture can be thickened, for example in vacuo at slightly elevated temperature (up to at most 80"C) until it can still be taken up with another solvent without problems.
  • the final curing of the resinous dental compositions according to the invention or of the dental materials resulting therefrom is carried out either thermally or photochemically in the case of one-component systems and by mixing the individual components in the case of self-curing multicomponent systems.
  • the organic network is constructed.
  • ring systems which are cationically polymerisable by ring opening, such as, for example, spiro-orthoesters, spiro-orthocarbonates, bicyclic spiro-orthoesters, mono- or oligoepoxides.
  • Suitable photoinitiators are, for example, compounds which on irradiation release acids, such as, for example, C 6 H5-N 2 BF 4 , o-
  • all photoinitiators are suitable which are employed for the polymerisation of oxirane-containing molecules, such as, for example, cycloaliphatic epoxides.
  • the triarylsulphonium salt is subjected to photolysis under the influence of irradiation and a Broensted acid is formed which catalyses the ring opening of the spiro groups, the resinous dental composition polymerising.
  • thermal initiators are added thereto.
  • Suitable thermal initiators are, for example, BF 3 as BF 3 ⁇ 2NC2H5, ZnCl2, TiCl 4 or SnCl2-
  • all the thermal initiators which are suitable for the polymerisation of epoxide groups can be employed.
  • the initiators are added in customary amounts.
  • the photoinitiators employed can be, for example, those commercially available. Examples of these are Iracure 184
  • Iracure 500 (1- hydroxycyclohexyl phenyl ketone/benzophenone) and other photoinitiators of the Iracure type obtainable from Ciba-Geigy; Darocure 1173, 1116, 1398, 1174 and 1020 (obtainable from Merck) , benzophenone, 2-chlorothioxanthone, 2- methylthioxanthone, 2-isopropylthioxanthone, benzoin, 4,4'- dimethoxybenzoin, camphorquinone and others.
  • thermal initiators are in particular organic peroxides in the form of diacyl peroxides, peroxydicarbonates, alkyl peresters, dialkyl peroxides, perketals, ketone peroxides and alkyl hydroperoxides.
  • thermal initiators are dibenzoyl peroxide, t-butyl perbenzoate and azobisisobutyronitrile.
  • the resinous dental compositions according to the invention can either be processed as such or together with the additives customary for dental materials described at the beginning, such as, for example, fillers, adhesion promoters or pigments to give pasty, photochemically and/or thermally curable dental materials.
  • the advantageous properties already mentioned of the cured resinous dental compositions according to the invention are still further improved by addition of fillers, so that dental materials result therefrom whose property profile is very considerably improved compared to the prior art, and which can be aimed at all requirements which are made of such materials.
  • Fillers employed can be, for example, macrofillers (of glass, ceramic or quartz, particle sizes between 2 and 50 ⁇ m) , homogeneous microfillers (for example of pyrogenic silica, particle sizes about 0.04 ⁇ m) , inhomogeneous microfillers (a part of the pyrogenic silica is present as a chip polymer) , hybrid fillers (mixture of macro- and microfillers) or very fine hybrid fillers (for example mixture of Aerosil and Ba or Sr glass with particle sizes of 2 ⁇ m) .
  • the mechanical properties of the resulting cured dental materials are additionally influenced by the particle size and the amount of the fillers.
  • the shrinkage (the higher the filler content in the same matrix, the lower the shrinkage) , the X-ray opacity (by addition of, for example, Ba, Sr, Ti or Zr components in the filler) and the thermal expansion coefficient (depending on the filler content; fillers usually have a lower expansion coefficient than the organic matrix) are also additionally positively influenced by the addition of fillers.
  • the resinous dental composition according to the invention for the preparation of dental materials to the uncured resinous dental compositions according to the invention in finely divided form as a filler.
  • the resinous dental composition according to the invention is polymerised, for example in the form of an emulsion, a precipitation, a solution or a suspension polymerisation. The polymer is dried, optionally finely ground and added to the resinous dental composition.
  • the resinous dental compositions according to the invention can not only be processed to give photochemically and/or thermally curable dental materials, it is also possible to prepare the self-curing multicomponent systems mentioned at the beginning from the resinous dental compositions according to the invention.
  • the dental materials prepared from the resinous dental compositions according to the invention comprise 20 to 100% by volume of the resinous dental compositions according to the invention, the remaining amounts are optionally resinous dental compositions according to the prior art, fillers, pigments, initiators, other customary additives or further copolymerisable monomers, such as, for example, acrylates, methacrylates, mono- or oligoepoxides, vinyl ethers, spiro- orthoesters, spiro-orthocarbonates, bicyclic spiro-orthoesters or methacryloyl spiro-orthoesters. It is preferred if the resulting dental materials comprise 30 to 70% by volume of the resinous dental compositions according to the invention.
  • the resinous dental compositions according to the invention can also be employed either as such or in the form of solutions as adhesives or adhesion promoters to enamel and dentine, for the surface-sealing of conventional composites, as adhesion promoters for dental fillers and very generally as a coating composition in the dental field.
  • a great advantage of the resinous dental compositions according to the invention compared to the prior art is that in the case of polymerisable, toxic monomers, for example of toxic acrylates or methacrylates, these can be bonded firmly to the silanes of the formula (II) and are thus firmly embedded in the inorganic/organic network, so that even in the case of incomplete polymerisation after the curing of the resinous dental composition no free monomers can be present.
  • toxic monomers for example of toxic acrylates or methacrylates
  • these can be bonded firmly to the silanes of the formula (II) and are thus firmly embedded in the inorganic/organic network, so that even in the case of incomplete polymerisation after the curing of the resinous dental composition no free monomers can be present.
  • based on acrylates or methacrylates there is, however, always the risk that after curing as a result of incomplete polymerisation free monomers are still present, which can lead to considerable toxic problems.
  • Example 1 Preparation of 2-trimethoxysilylpropyl methyl ether-1,4,6-trioxaspiro[4.4]-nonane
  • Example 2 Hydrolytic condensation of 2-trimethoxy- silylpropyl methyl ether-1,4,6-trioxaspiro[4.4]nonane 20 mg of triethyla ine and 0.54 g (30 mol) of H20 are added dropwise to 6.54 g (20 mol) of spirosilane according to Example 1 for the hydrolysis and condensation of the -Si(OCH 3 ) 3 groups.
  • Example 3 Cationic polymerisation of the spirosiloxane from Example 2
  • the spirosiloxane according to Example 2 is treated with 2% starter (UVI 6990 from Union Carbide) , applied to KBr discs, freed from all volatile constituents and irradiated with UV light (UV "Blue Point” point irradiator from Dr. K. H ⁇ nle) , i.e. cured by polymerisation (complete conversion after ⁇ 1 min) .
  • UV light UV "Blue Point” point irradiator from Dr. K. H ⁇ nle
  • Example 4 Cationic polymerisation of the spirosiloxane from Example 2
  • the spirosiloxane according to Example 2 is treated with 2% starter (KI-85 from Degussa) and applied to glass slides.
  • 2% starter KI-85 from Degussa
  • a film-drawing frame having various gap widths (30 and 80 ⁇ m) is used.
  • the volatile constituents are removed, and curing is carried out by means of a "UVALOC 1000" UV irradiator from Loctite.
  • Example 5 Synthesis procedure for a resin system based on TMPTA and mercaptopropylmethyldimethoxysilane (ratio of 1:1)
  • Example 6 Synthesis procedure for a resin system based on Ebercryl-53 and mercaptopropyl-methyldimethoxysilane (ratio
  • Example 7 Synthesis procedure for a resin system based on TMPTA and ( ercaptomethyl)methyl-diethoxysilane (ratio of 1.2:1)
  • Example 8 Synthesis procedure for a resin system based on TMPTA and (mercaptomethyl)methyl-diethoxysilane (ratio of 1:1)
  • Example 9 Synthesis procedure for a resin system based on TMPTA and (mercaptomethyl)-dimethylmethoxysilane (ratio 1:1)
  • 0.3 mol of (mercaptomethyl)dimethylmethoxysilane is added dropwise under a protective gas atmosphere to an initial mixture of 0.3 mol of trimethylolpropane triacrylate (TMPTA) in 270 ml of ethyl acetate.
  • TMPTA trimethylolpropane triacrylate
  • a solution of 0.168 g (0.003 mol) of KOH in ethanol is slowly added dropwise. After about 5 minutes the reaction (thiol addition) is complete.
  • 5.4 g of 0.7 N HCl are added dropwise for the hydrolysis and condensation of the methoxy groups.
  • Working up is carried out after stirring at room temperature for 20 hours by extracting by shaking, first with dilute, aqueous NaOH and finally with distd. water.
  • the viscosity is variable from 900 to 7,200 mPa.s at 25 ⁇ C by means of the synthesis conditions (resin system E) .
  • Example 10 Synthesis procedure for a resin system based on TMPTMA and mercaptopropylmethyl-dimethoxysilane (ratio of 1:1)
  • mercaptopropylmethyldi- methoxysilane 18.03 g (0.1 mol) of mercaptopropylmethyldi- methoxysilane are added dropwise under a protective gas atmosphere to an initial mixture of 33.84 g (0.1 mol) of trimethylolpropane trimethacrylate (TMPTMA) in 100 ml of ethyl acetate. With cooling (ice-bath), a solution of 0.56 g (0.01 mol) of KOH in ethanol is slowly added dropwise. After about 5 minutes the reaction (thiol addition) is complete. 1.8 g of 5.7 N HCl are added dropwise for the hydrolysis and condensation of the methoxy groups.
  • TMPTMA trimethylolpropane trimethacrylate
  • Example 11 Synthesis procedure for a resin system based on TMPTMA and ercaptopropyl-trimethoxysilane (ratio of 1:1)
  • Example 12 Synthesis procedure for a resin system based on BADMA and (mercaptomethyl)-methyldiethoxysilane (ratio of 1:1) 0.05 mol of (mercaptomethyl)methyldiethoxysilane is added dropwise under a protective gas atmosphere to an initial mixture of 0.05 mol of bisphenol-A-dimethacrylate (BADMA) in 50 ml of ethyl acetate. With cooling (ice-bath) , a solution of 0.28 g (0.005 mol) of KOH in ethanol is slowly added dropwise. After about 1 minute, the reaction (thiol addition) is complete. 2.16 g of 2.4 N HCl are added dropwise for the hydrolysis and condensation of the methoxy groups.
  • BADMA bisphenol-A-dimethacrylate
  • Example 13 Synthesis procedure for a resin system based on Plex 6833-0 and mercaptopropyl- ethyldimethoxysilane (ratio of 1:1)
  • 0.05 mol of mercaptopropylmethyldimethoxysilane is added dropwise under a protective gas atmosphere to an initial mixture of 0.05 mol of ethoxylated bisphenol-A-dimethacrylate (Plex 6833-0) in 50 ml of ethyl acetate.
  • ethoxylated bisphenol-A-dimethacrylate Plex 6833-0
  • a solution of 0.28 g (0.005 mol) of KOH in ethanol is slowly added dropwise. After about 1 minute the reaction (thio addition) is complete.
  • 2.16 g of 2.4 N HCl are added dropwise for the hydrolysis and condensation of the methoxy groups.
  • Example 14 Synthesis procedure for a resin system based on TMPTA and (mercaptomethyl)-methyldiethoxysilane (ratio of 1.2:1) silanised with trimethylchlorosilane
  • the aim of the silanisation is the reaction of the free SiOH groups (hydrophilic centres in the resin) to reduce the absorption of water and thus to reduce the decrease in strength due to the addition of water, and to reduce the resin viscosity in order finally to ensure a higher filler content in the composite.
  • Example 15 Synthesis procedure for a resin system based on TMPTA and (mercaptomethyl)methyldiethoxysilane and mercaptopropyltrimethoxysilane (ratio of 1.2 : 0.5 : 1)
  • the resin viscosity which is important for the workability (for example for the production of moulded articles and for the incorporation and the content of the fillers) can be varied within wide ranges, as is confirmed by these exemplary embodiments, with the same composition by means of the synthesis conditions and by the starting material combination and can thus be suited to the requirements of the particular application case.
  • the incorporation can be carried out, for example, using the AM 501 universal mixer from Hauschild.
  • Resin system LI Resin system K is mixed with 75% by weight (60% by volume) of the abovementioned filler mixture.
  • Resin system L2 Resin system B is mixed with 75% by weight (60% by volume) of the abovementioned filler mixture.
  • Resin system L3 Resin system I is mixed with 75% by weight (60% by volume) of the abovementioned filler mixture.
  • UV-cured moulded articles for other investigations are prepared from the resin systems A to M after addition of 1.0% of Iracure 184R as a UV initiator.
  • Iracure 184R as a UV initiator.
  • Corresponding curing in the visible spectral range (after addition of, for example, camphorquinone as initiator) is likewise possible.
  • Breaking strength The breaking strength is deter ⁇ mined in a 3-point flexural test (UTS-100 universal testing machine) on rectangular rods (2x2x25mm) .
  • E Modulus The E modulus is determined in a
  • Shrinkage on curing is determined by means of the difference in thickness before and 24 h after curing.
  • Water absorption The water absorption is determined on cylindrical moulded articles (1 mm thick with a diameter of 10 mm) after storage for 14 days in distd. water at 40°C by final weighing (corrected for the water solubility) .
  • Water solubility The water solubility is determined on cylindrical moulded articles (1 mm thick with a diameter of 10 mm) after storage for 14 days in distd. water at 40°C by final weighing.
  • the shrinkage on curing can be reduced further by the use or by the addition of silanes of the general formula (I) .
  • Example 17 Preparation of a composite which is photochemically curable in the visible spectral range based on resin system K
  • Example 19 Preparation of a composite which is photochemically curable in the visible spectral range based on resin system K (without fillers)

Landscapes

  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Chemical & Material Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Epidemiology (AREA)
  • Organic Chemistry (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dental Preparations (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP92922122A 1991-10-09 1992-10-07 Dentalharzmasse auf basis von polymerisierbaren polysiloxanen Expired - Lifetime EP0643752B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4133494A DE4133494C2 (de) 1991-10-09 1991-10-09 Dentalharzmasse, Verfahren zu deren Herstellung und deren Verwendung
DE4133494 1991-10-09
PCT/US1992/008530 WO1993007230A1 (en) 1991-10-09 1992-10-07 Resinous dental composition based on polymerisable polysiloxanes

Publications (3)

Publication Number Publication Date
EP0643752A4 EP0643752A4 (de) 1994-06-03
EP0643752A1 true EP0643752A1 (de) 1995-03-22
EP0643752B1 EP0643752B1 (de) 1999-09-15

Family

ID=6442372

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92922122A Expired - Lifetime EP0643752B1 (de) 1991-10-09 1992-10-07 Dentalharzmasse auf basis von polymerisierbaren polysiloxanen

Country Status (11)

Country Link
US (1) US5877232A (de)
EP (1) EP0643752B1 (de)
AT (1) ATE184627T1 (de)
AU (1) AU2767492A (de)
CA (1) CA2120490C (de)
DE (2) DE4133494C2 (de)
DK (1) DK0643752T3 (de)
ES (1) ES2135417T3 (de)
GR (1) GR3031475T3 (de)
PT (1) PT100951B (de)
WO (1) WO1993007230A1 (de)

Families Citing this family (50)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4310733A1 (de) * 1993-04-01 1994-10-06 Fraunhofer Ges Forschung Selbsthärtende Systeme
DE19617876A1 (de) * 1996-04-24 1997-11-06 Ivoclar Ag Polymerisierbares Dentalmaterial
DE19619046A1 (de) * 1996-05-02 1997-11-06 Ivoclar Ag Verwendung einer Zusammensetzung als Dentalmaterial und Dentalmaterial
DE19648283A1 (de) 1996-11-21 1998-05-28 Thera Ges Fuer Patente Polymerisierbare Massen auf der Basis von Epoxiden
US6096903A (en) 1997-03-25 2000-08-01 Ivoclar Ag Hydrolysable and polymerizable oxetane silanes
DE19714324B4 (de) * 1997-03-25 2004-09-02 Ivoclar Vivadent Ag Hydrolysierbare und polymerisierbare Oxetansilane
DE19807631A1 (de) * 1998-02-23 1999-08-26 Agfa Gevaert Ag Härtbare Dentalmassen
DE19846556A1 (de) 1998-10-09 2000-04-13 Degussa Dentalwerkstoff aufweisend poröse Glaskeramiken, poröse Glaskeramiken, Verfahren und Verwendung
US6458865B2 (en) 1999-01-15 2002-10-01 Curators Of The University Of Missouri Photopolymerizable vinyl ether based monomeric formulations and polymerizable compositions which may include certain novel spiroorthocarbonates
US6569917B1 (en) 1999-01-21 2003-05-27 Ivoclar Ag Dental materials based on polysiloxanes
DE19903177C5 (de) * 1999-01-21 2010-09-16 Ivoclar Vivadent Ag Verwendung von Materialien auf der Basis von Polysiloxanen als Dentalmaterialien
WO2001012679A1 (de) * 1999-08-13 2001-02-22 Deltamed Medizinprodukte Gmbh Mit sichtbarem licht aushärtende zusammensetzung und deren verwendung
KR100735960B1 (ko) 1999-09-10 2007-07-06 나그라카드 에스.에이. 데이터베이스용 메시지 전송 처리 방법 및 그 시스템
US6610759B1 (en) 2000-03-06 2003-08-26 Curators Of The University Of Missouri Cationically polymerizable adhesive composition containing an acidic component and methods and materials employing same
DE10016324A1 (de) * 2000-03-31 2001-10-11 Roehm Gmbh Ormocere, Verfahren zu deren Herstellung sowie Verwendung
DE10021605A1 (de) * 2000-05-04 2001-11-08 Upmeyer Hans Juergen Füllmaterial für Zähne
EP1307172B1 (de) * 2000-08-11 2006-06-07 Dentsply International, Inc. Polyaminoestern und deren verwendung zur herstellung von dentalmassen
US7101942B2 (en) 2001-01-19 2006-09-05 Ivoclar Vivadent Ag Dental materials based on metal oxide clusters
WO2002088222A1 (de) 2001-03-13 2002-11-07 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. Phosphorhaltige, organisch polymerisierbare silane und damit hergestellte kieselsäure-polykondensate
DE10114290B4 (de) 2001-03-23 2004-08-12 Ivoclar Vivadent Ag Desktop-Verfahren zur Herstellung von Dentalprodukten unter Verwendung des 3D-Plottings
WO2003013444A1 (en) 2001-08-10 2003-02-20 Dentsply International Inc. One-part self-priming dental adhesive
US20030199605A1 (en) * 2002-04-23 2003-10-23 Fischer Dan E. Hydrophilic endodontic sealing compositions and methods for using such compositions
US20050059752A1 (en) * 2002-07-12 2005-03-17 Rhodia Chimie Stable, cationically polymerizable/crosslinkable dental compositions having high filler contents
DE10339912B4 (de) 2003-08-29 2016-07-21 Ivoclar Vivadent Ag Dentale Beschichtungsmaterialien, deren Verwendung sowie Verfahren zur Beschichtung einer Substratoberfläche
DE102005018059A1 (de) 2003-10-24 2006-10-26 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zum Verbrücken von Hydroxy- oder Carbonsäuregruppen enthaltenden, organisch polymerisierbaren Silanen oder Silanharzeinheiten, sowie Produkte dieses Verfahrens
DE10349766A1 (de) 2003-10-24 2005-06-16 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Kieselsäurepolykondensate mit verzweigtkettigen, urethan-, säureamid- und/oder carbonsäureestergruppenhaltigen Resten
US7173075B2 (en) * 2004-08-30 2007-02-06 Ultradent Products, Inc. Gas releasing sealing and filling compositions
DE102005018351B4 (de) 2005-04-20 2008-05-29 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verwendung widerstandsfähiger, langlebiger Komposite im Dentalbereich
US7828550B2 (en) * 2005-09-21 2010-11-09 Ultradent Products, Inc. Activating endodontic points and dental tools for initiating polymerization of dental compositions
DE102007035734A1 (de) 2006-08-29 2008-03-20 Ivoclar Vivadent Ag Dentalmaterialien mit geringem Polymerisationsschrumpf
EP1905415B1 (de) 2006-09-27 2009-07-01 Ivoclar Vivadent AG Polymerisierbare Zusammensetzungen mit Acylgermanium-Verbindungen als Initiatoren
US20090075235A1 (en) * 2006-10-27 2009-03-19 Letcher William F Fixed, Implant-Supported, Full Arch Dental Prosthetics and Methods of Seating Thereof
US20090017421A1 (en) * 2006-10-27 2009-01-15 Letcher William F Method of Preparing an Artificial Dental Prosthetic and Seating Thereof
US7758346B1 (en) 2006-10-27 2010-07-20 Letcher William F Implant prosthodontics and methods of preparing and seating the same
EP2103297B1 (de) 2008-03-20 2012-05-16 Ivoclar Vivadent AG Polymerisierbare Zusammensetzung mit mehrere Germanium-Atome enthaltenden Initiatoren
EP2151214B1 (de) * 2008-07-30 2013-01-23 Ivoclar Vivadent AG Lichthärtende Schlicker für die stereolithographische Herstellung von Dentalkeramiken
JP5269734B2 (ja) * 2008-10-16 2013-08-21 株式会社デンソー 重合硬化性組成物、その重合硬化方法、および重合硬化樹脂組成物
DE102009035970A1 (de) 2009-08-04 2011-02-17 Heraeus Kulzer Gmbh Antimikrobiell ausgestattete Dentalmaterialien, insbesondere zur Verhinderung von Plaqueanlagerungen
JP5055397B2 (ja) * 2010-03-10 2012-10-24 株式会社ユニックスジャパン 歯科用成形体、及び歯科用樹脂材料
KR101071554B1 (ko) * 2010-04-06 2011-10-10 주식회사 하스 세라믹 유치관 제조방법 및 이에 의해 제조된 세라믹 유치관
US20140080082A1 (en) * 2012-09-14 2014-03-20 Orthoaccel Technologies Inc. Light cure bite plate for orthodontic remodeling devices
DE102013008176A1 (de) 2012-10-05 2014-04-10 Voco Gmbh Kit und Verfahren zur indirekten chairside Herstellung von Kompositinlays
DE102014116402A1 (de) 2014-11-11 2016-05-12 Voco Gmbh Verwendung radikalisch härtbarer Zusammensetzungen in generativen Fertigungsverfahren
DE102014116389A1 (de) 2014-11-11 2016-05-12 Voco Gmbh Radikalisch härtbare dentale Zusammensetzungen
DE102015112800A1 (de) 2015-04-09 2016-10-13 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Mehrteilig aufgebaute Dentalprothese sowie Verfahren und Vorrichtung zu ihrer Herstellung
DE102015114397A1 (de) 2015-08-28 2017-03-02 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Misch- und Formverfahren für gefüllte Duromere aus organisch vernetzbaren Kompositmassen, insbesondere für dentale Zwecke
KR102470542B1 (ko) * 2017-04-28 2022-11-24 (주) 개마텍 광경화 코팅용 조성물 및 코팅막
EP3660087B1 (de) 2018-11-29 2024-05-29 Ivoclar Vivadent AG Verfahren und werkstoff zur herstellung von 3d objekten durch energieimpuls-induzierten transferdruck
EP3660085A1 (de) 2018-11-29 2020-06-03 Ivoclar Vivadent AG Stützmaterial für den energieimpuls-induzierten transferdruck
DE102019122174A1 (de) 2019-08-19 2021-02-25 Voco Gmbh Dentale polymerisierbare Zusammensetzung auf der Basis kondensierter Silane

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0261520A2 (de) * 1986-09-26 1988-03-30 Bayer Ag (Meth)-acrysäureester von Tricyclodecangruppen enthaltenden Siloxanen
DE4125201C1 (de) * 1991-07-30 1992-10-01 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung Ev, 8000 Muenchen, De

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3127363A (en) * 1955-08-05 1964-03-31 Process for the manufacture of elasto-
US4387240A (en) * 1978-06-02 1983-06-07 Minnesota Mining And Manufacturing Company Oligomeric methacryl substituted alkylsiloxanes
JPS55137178A (en) * 1979-04-11 1980-10-25 Kanebo Ltd Adhesive material for rigid living tissue
DE3031894A1 (de) * 1980-08-23 1982-09-16 Bayer Ag, 5090 Leverkusen Vinylsilikon-pasten fuer die zahnabformung
US4368314A (en) * 1980-08-29 1983-01-11 Toagoesi Chemical Industry Co., Ltd. Curable composition comprising spiro-orthoester compound
US4504231A (en) * 1981-02-17 1985-03-12 Dentsply Research & Development Corp. Process for filling teeth
JPS6067531A (ja) * 1983-09-22 1985-04-17 Toshiba Corp 樹脂組成物
JPS61227509A (ja) * 1985-04-02 1986-10-09 G C Dental Ind Corp 歯科用修復材
US4673354A (en) * 1985-10-01 1987-06-16 Minnesota Mining And Manufacturing Company Stable silanol priming solution for use in dentistry
DE3903407A1 (de) * 1989-02-06 1990-08-09 Blendax Werke Schneider Co Dentales fuellungsmaterial
DE3913250A1 (de) * 1989-04-22 1990-10-25 Degussa Dentalmaterial (ii)
DE3913252A1 (de) * 1989-04-22 1990-10-25 Degussa Dentalmaterial (i)
DE4011044A1 (de) * 1990-04-05 1991-10-10 Fraunhofer Ges Forschung Silane, verfahren zu ihrer herstellung und ihre verwendung zur herstellung von polymerisaten und polykondensaten

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0261520A2 (de) * 1986-09-26 1988-03-30 Bayer Ag (Meth)-acrysäureester von Tricyclodecangruppen enthaltenden Siloxanen
DE4125201C1 (de) * 1991-07-30 1992-10-01 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung Ev, 8000 Muenchen, De
EP0525392A1 (de) * 1991-07-30 1993-02-03 Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. Hydrolysierbare und polymerisierbare Silane

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9307230A1 *

Also Published As

Publication number Publication date
AU2767492A (en) 1993-05-03
PT100951A (pt) 1993-11-30
JP3606325B2 (ja) 2005-01-05
DE69230006T2 (de) 2000-04-20
DE69230006D1 (de) 1999-10-21
ATE184627T1 (de) 1999-10-15
US5877232A (en) 1999-03-02
WO1993007230A1 (en) 1993-04-15
CA2120490C (en) 1998-01-27
DE4133494A1 (de) 1993-04-15
GR3031475T3 (en) 2000-01-31
EP0643752B1 (de) 1999-09-15
JPH07504157A (ja) 1995-05-11
DK0643752T3 (da) 1999-12-20
PT100951B (pt) 1999-07-30
DE4133494C2 (de) 1996-03-28
CA2120490A1 (en) 1993-04-15
ES2135417T3 (es) 1999-11-01
EP0643752A4 (de) 1994-06-03

Similar Documents

Publication Publication Date Title
EP0643752B1 (de) Dentalharzmasse auf basis von polymerisierbaren polysiloxanen
AU753359B2 (en) Cyclosiloxane-based cross-linkable monomers, production thereof and use thereof in polymerisable materials
US6096903A (en) Hydrolysable and polymerizable oxetane silanes
AU2009202780B2 (en) Dental adhesive composition
JP3609706B2 (ja) メチレンジチエパンに基づく加水分解可能および重合可能なシラン
CA2296227C (en) Dental materials based on polysiloxanes
CA2204234C (en) Dental material
US7470728B2 (en) Dental glazes and method of manufacture and use thereof
EP0368657A2 (de) Dentales Restaurationsmaterial
US5674964A (en) Self-curing systems
US7893129B2 (en) Stable, cationically polymerizable/crosslinkable dental compositions
CA2232960C (en) Hydrolysable and polymerizable oxetane silane
US7893130B2 (en) Photocurable dental composition
Moszner et al. Sol‐Gel Materials, 1. Synthesis and Hydrolytic Condensation of New Cross‐Linking Alkoxysilane Methacrylates and Light‐Curing Composites Based upon the Condensates
CA2232915C (en) Hydrolysable and polymerizable vinylcyclopropane silanes
US7101942B2 (en) Dental materials based on metal oxide clusters
CA2433506A1 (en) Process for the preparation of a polymerisable dental composition
JP3606325B6 (ja) 重合性ポリシロキサン類に基づく樹脂歯科組成物
JP4723379B2 (ja) 高い充填剤含有量を有する安定な陽イオン重合性／架橋性歯科用組成物
AU2004321434A1 (en) Dental composition containing unsaturated carbosilane containing components
JP2008505940A (ja) 不飽和ハロゲン化アリールアルキルエーテル成分を含む歯科用組成物

Legal Events

Date Code Title Description
A4 Supplementary search report drawn up and despatched
AK Designated contracting states

Kind code of ref document: A4

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU NL SE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19940325

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU NL SE

17Q First examination report despatched

Effective date: 19961121

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU NL SE

REF Corresponds to:

Ref document number: 184627

Country of ref document: AT

Date of ref document: 19991015

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: RITSCHER & SEIFERT

REF Corresponds to:

Ref document number: 69230006

Country of ref document: DE

Date of ref document: 19991021

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2135417

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: REITH, HANS-JOACHIM, DR.

Effective date: 20000614

NLR1 Nl: opposition has been filed with the epo

Opponent name: REITH, HANS-JOACHIM, DR.

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PLBO Opposition rejected

Free format text: ORIGINAL CODE: EPIDOS REJO

PLBN Opposition rejected

Free format text: ORIGINAL CODE: 0009273

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: OPPOSITION REJECTED

27O Opposition rejected

Effective date: 20030412

NLR2 Nl: decision of opposition

Effective date: 20030412

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20100923

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20101029

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20101016

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 20110926

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20111005

Year of fee payment: 20

Ref country code: GB

Payment date: 20110930

Year of fee payment: 20

Ref country code: GR

Payment date: 20110929

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IE

Payment date: 20111005

Year of fee payment: 20

Ref country code: ES

Payment date: 20111020

Year of fee payment: 20

Ref country code: LU

Payment date: 20111020

Year of fee payment: 20

Ref country code: NL

Payment date: 20111020

Year of fee payment: 20

Ref country code: CH

Payment date: 20111026

Year of fee payment: 20

Ref country code: SE

Payment date: 20111006

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20111108

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69230006

Country of ref document: DE

REG Reference to a national code

Ref country code: DK

Ref legal event code: EUP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69230006

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: V4

Effective date: 20121007

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

BE20 Be: patent expired

Owner name: THE *PROCTER & GAMBLE CY

Effective date: 20121007

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20121006

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

REG Reference to a national code

Ref country code: GR

Ref legal event code: MA

Ref document number: 990402566

Country of ref document: GR

Effective date: 20121008

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK07

Ref document number: 184627

Country of ref document: AT

Kind code of ref document: T

Effective date: 20121007

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20121006

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20130702

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20121008

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20121007